CN102219205A - Separation method for metallic and semiconducting single-walled carbon nanotubes - Google Patents
Separation method for metallic and semiconducting single-walled carbon nanotubes Download PDFInfo
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- CN102219205A CN102219205A CN 201110066035 CN201110066035A CN102219205A CN 102219205 A CN102219205 A CN 102219205A CN 201110066035 CN201110066035 CN 201110066035 CN 201110066035 A CN201110066035 A CN 201110066035A CN 102219205 A CN102219205 A CN 102219205A
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Abstract
The invention relates to a separation method for metallic and semiconducting single-walled carbon nanotubes, which selects agarose gel with different pore sizes as a chromatographic column packing material and uses different mobile phases to realize the separation of the metallic and semiconductor single-walled carbon nanotubes according to the length distribution of the single-walled carbon nanotubes, wherein the chromatographic column is a (200-300) mm*(8-20) mm normal-pressure or medium-pressure chromatographic column; the pore size of the agarose gel can be 45-200 mu m; the packing height of the agarose gel is 6-25 cm; and the chromatographic column packing material is slowly pushed into the chromatographic column by a plurality of times and the chromatographic column is vertically placed until the agarose gel reaches the packing height and no air bubble generates. The separation method is simple to operate, has low cost and narrow distribution range of separation samples, is beneficial to large-scale separation, not only successfully separates the metal and non-metallic single-walled carbon nanotubes, and but also achieves the successful separation of the single-walled carbon nanotubes with different length distribution.
Description
Technical field
The present invention relates to the separation method of a kind of metallicity and semi-conductive single-walled carbon nanotubes, particularly relate to from Single Walled Carbon Nanotube, isolate clear and legiblely, the method for structure is single and electrical properties is stable Single Walled Carbon Nanotube.
Background technology
Lijima in 1991 finds that carbon nanotube is the C that continues
60The another great discovery that catches people's attention in carbon geochemistry field since the discovery.Carbon nanotube (carbon nanotubes is called for short CNTs) can be regarded curling seamless, the hollow tube that forms of Graphene lamella that six-ring is formed as, this particular structure feature makes it have special electrical properties and superpower mechanical property, demonstrates good prospects for application at aspects such as electron device, matrix material, hydrogen storage material, chemistry and biosensors.
It is exactly separating of CNTs that yet these researchs face a huge challenge with application.Because that the existing preparation technology obtains all is the polydisperse CNTs of structure and performance, the CNTs mixture of various structures and performance has limited its further research and application in fields such as molectronics and photoelectricities widely.
Single Walled Carbon Nanotube (single wall carbon nanotubes is called for short SWNTS) is to be made of individual layer cylinder shape graphite linings, and the distribution range of its diameter is little, and defective is few, has higher uniformity consistency.The electrical properties of Single Walled Carbon Nanotube is by its diameter and chiral angle decision.For semiconductor single-walled carbon, the variation that can be with is along with the change of diameter is opposite.And for metallicity and semiconducting nanotubes, the main optical transition that takes place vibrates along with diameter and chirality and changes.Single Walled Carbon Nanotube generates the metallicity and the semi-conductive single-walled carbon nanotubes of different lengths usually simultaneously in process of growth.The difference of Single Walled Carbon Nanotube attribute can cause the instability and the inefficient field mobility of electrology characteristic, and then causes the productive rate of high precision electron device to reduce.And the difference of length can cause different biological toxicity performances.
So, in order to realize that based on the application of Single Walled Carbon Nanotube electrology characteristic and the accurate protection of biological toxicity performance the most key task is to obtain length and the accurate controlled Single Walled Carbon Nanotube of attribute.Break through though indented material has obtained some, show in the energy growth phase feasible narrow chirality distribution Single Walled Carbon Nanotube formula.It is exactly separating of CNTs that yet these researchs face a huge challenge with application.Because that the existing preparation technology obtains all is structure and the performance CNTs that distribute more, the CNTs mixture of various structures and performance has limited its further research and application in fields such as molectronics and photoelectricities widely.
In order to break through this problem, adopted several different methods that carbon nanotubes grown is separated, such as, the atom electricity is led separation, and selective oxidation separates, electron puncture, ultracentrifuge separates and separates with the field flow instrument, chromatography is separated.Tanaka(Takeshi Tanaka wherein, Yasuko Urabe, Daisuke Nishide, Hiromichi Kataura1, Continuous Separation of Metallic and Semiconducting Carbon Nanotubes Using Agarose Gel, Applied Physics Express 2 (2009) 125002) it is the most close to adopt sepharose to isolate metal and nonmetallic Single Walled Carbon Nanotube and the inventive method principle in syringe.This method has been filled the high gel of 3-5cm in syringe, manually add moving phase.This method can only be carried out simple separation to a small amount of, lower concentration carbon nanotube.Syringe can not seal, moving phase can not continue, uninterruptedly, at the uniform velocity controlled adding.
In addition.Patent CN200610113211.1 adopts photoetching method to prepare gold electrode on silica containing substrate, utilizing focused ion beam to carve several gaps on electrode is immersed in the DMF solution of Single Walled Carbon Nanotube, in 2～8V, frequency is under the electric field action of 1～10Hz, with metallicity and semi-conductive single-walled carbon nanotubes separated in synchronization.
Among the patent CN200710159924.6, mainly carbon nanotube is dispersed in the medium through chemistry or biological method modification, adopts the carbon nanotube separation of sorbent material again particular modification.
Patent CN200910182678.5 adopts electrophoresis, the centrifugal or method freezing to push, the selection adsorptivity and the inrichment of separating with medium and metallicity or semiconductive carbon nano tube form semiconductive carbon nano tube and metallic carbon nanotubes enrichment region, realize separating of metallicity and semiconductive carbon nano tube.
If yet be amplified to industrial scale for these methods, on productive rate, purity, cost, all more or less there are some problems.
Summary of the invention
This patent adopts the gel chromatography method, directly separates the metallicity and the semi-conductive single-walled carbon nanotubes dispersion of non-modified.Advantage is simple to operate, and cost is low, and the sample separation narrow distribution range is beneficial to extensive separation.
The present invention adopts sepharose to make the chromatogram column packing, selects the sepharose of different aperture sizes to come the preparative chromatography post.The result not only successfully isolates metallicity and semi-conductive single-walled carbon nanotubes, and has successfully realized the separation by the Single Walled Carbon Nanotube of different lengths distribution.
The present invention realizes like this.
The separation method of metallicity of the present invention and semi-conductive single-walled carbon nanotubes is characterized in that:
Described method selects the sepharose in different apertures to make the chromatogram column packing, adopts different moving phase, separating by Single Walled Carbon Nanotube length distribution, realization metallicity and semi-conductive single-walled carbon nanotubes.
In concrete enforcement,
Described chromatographic column is normal pressure or the medium pressure chromatography post of mm of (200-300) mm * (8-20).
Described sepharose aperture can be 45-200 μ m, preferred 60-165 μ m.
Described sepharose packing height is 6-25 cm, preferred 10-20cm.
Described chromatographic column filler is repeatedly pushed chromatographic column slowly, chromatographic column is vertically placed, tamp until gel and reach the chromatographic column packing height and do not have bubble.
Described separation method specifically can comprise step down.
(1) carbon nanotube mother liquor preparation.
With the dispersion carbon nanotube of non-modified to be separated and concentration 0.5-3%, preferred 1.5% anion surfactant, preferably sodium dodecyl sulfate (SDS) or Sodium desoxycholate (DOC) thorough mixing is that carbon nanotube target volume concentration is the mixture of 0.02-1.0mg/mL, preferred 0.3 mg/mL, through the 400kW ultra-sonic dispersion after 2～6 hours, preferred 5 hours, centrifugation goes out upper strata liquid as the carbon nanotube mother liquor that carries out gel chromatography separation again.
(2) gel chromatography separation.
Anion surfactant, preferably sodium dodecyl sulfate or the Sodium desoxycholate that at first adopts 0.5-3 wt% is moving phase, and flow rate pump 0.1mL/min-0.5mL/min, preferred 0.1mL/min washed populated gel chromatographic columns 1 hour.
In gel chromatographic columns, add the carbon nanotube mother liquor that 0.2mL-5mL, preferred 2mL step (1) obtain, adopting 0.5-3wt%, preferred 1.5% anion surfactant, preferably sodium dodecyl sulfate or Sodium desoxycholate is moving phase, flow rate pump 0.1-0.5mL/min, preferred 0.1mL/min, collect sample at set intervals, collected 0.5-3 hour, preferred 1 hour, and obtained the carbon nanotube of different lengths and semiconductive.
The present invention is dispersed in carbon nanotube in the medium, utilize the selection adsorptivity of medium and metallicity or semiconductive carbon nano tube, the gel pore size is realized separating of metallicity and semiconductive and different lengths carbon nanotube simultaneously to the selectivity physical adsorption of different length carbon nanotubes in the dependence chromatographic column.
Key point of the present invention is.
The preparation of sepharose stratographic.Not only to control
(1) the filling length of sepharose, and
(2) to control sepharose even, consistent distribution in chromatographic column, the more important thing is
(3) to guarantee there is not bubble in the chromatographic column.
Innovative point of the present invention.
1) adopts sepharose to make the filler packing and come separating carbon nano-tube.
2) adopt different moving phase to realize separating of metallicity and semi-conductive single-walled carbon nanotubes.
Description of drawings
Fig. 1. the present invention makes the synoptic diagram of chromatographic column by oneself.
Fig. 2 is the partial enlarged drawing of A among Fig. 1.
Among the figure: 1: lock screw; 2: nut; 3: Glass tubing; 4: moving phase; 5: kapillary; 6: seal washer; 7: the soft filter net; 8: the hard filtering net.
Embodiment
Chromatographic column of the present invention is filled as shown in Figure 1.Employing is of a size of that (200-300) mm * (8-20) normal pressure or the medium pressure chromatography post of mm are done chromatographic column, the sepharose gel (60 μ m-200 μ m) of varying particle size is repeatedly pushed chromatographic column slowly, chromatographic column is vertically placed, tamp until gel and to reach the chromatographic column packing height and not have bubble, by soft filter net 7, hard filtering net 8, seal washer 6, seal two ends, fastening nut and lock screw, standby.
Preparation were established of the present invention.
1. carbon nanotube mother liquor preparation.
(ultra-sonic dispersion certain mass carbon nanotube (0.02-1.0mg/mL), centrifugation go out upper strata liquid as the carbon nanotube mother liquor that carries out gel chromatography separation to the anion surfactant of employing concentration 0.5%-3%.
2. gel chromatography separation.
The anion surfactant that at first adopts 0.5-3 wt% is a moving phase, and flow rate pump 0.1mL/min-0.5mL/min washed populated chromatographic column 1 hour.
In chromatographic column, add the carbon nanotube mother liquor of 0.2mL-2mL, adopting sodium lauryl sulphate or the Sodium desoxycholate of 0.5-3wt% is moving phase, and flow rate pump 0.1mL/min-0.5mL/min collects sample at set intervals, collected 1 hour, and obtained the carbon nanotube of different lengths and semiconductive.
Embodiment 1
A: dispose 1 wt% DOC solution.
B: take by weighing the 0.0021g Single Walled Carbon Nanotube and join in the 10mL DOC aqueous solution, target volume concentration 0.2 mg/mL, the ultrasonic 4h that vibrates obtains mixed solution.With scattered mixed solution, high speed centrifugation 15 min get upper strata centrifugate, obtain the Single Walled Carbon Nanotube mother liquor again.
C: gel chromatography separation.
Draw 0.5 mL dispersing Nano carbon tubes mother liquor, be injected in the populated chromatographic column, as moving phase, flow velocity 0.2 mL/min of pump collects sample every 2min, collects 1 hour with 1 wt% DOC.
A: dispose 1.5 wt% SDS solution.
B: take by weighing 0.004 g Single Walled Carbon Nanotube and join in the 10 mL SDS aqueous solution, target volume concentration 0.4 mg/mL ultrasonic 6 h that vibrate obtain mixed solution.With scattered mixed solution, high speed centrifugation 15 min get upper strata centrifugate, obtain the Single Walled Carbon Nanotube mother liquor again.
C: gel chromatography separation.
Draw 0.5 mL dispersing Nano carbon tubes mother liquor, be injected in the populated chromatographic column, as moving phase, the flow velocity 0.1mL/min of pump collects sample every 2min, collects 1 hour with 1.5 wt% SDS.
Claims (10)
1. the separation method of metallicity and semi-conductive single-walled carbon nanotubes is characterized in that:
Described method selects the sepharose in different apertures to make the chromatogram column packing, adopts different moving phase, by Single Walled Carbon Nanotube length distribution, the separating of dispersion Single Walled Carbon Nanotube of realizing metallicity and semiconductive.
2. according to the separation method of the carbon nanotube of claim 1, it is characterized in that:
Described sepharose aperture is 45-200 μ m;
Described sepharose packing height is 6-25 cm.
3. according to the separation method of the carbon nanotube of claim 2, it is characterized in that:
Described sepharose aperture is 60-165 μ m;
Described sepharose packing height is 10-20 cm.
4. according to the separation method of the carbon nanotube of claim 2, it is characterized in that:
Described chromatographic column is normal pressure or the medium pressure chromatography post of mm of (200-300) mm * (8-20).
5. according to the separation method of the carbon nanotube of claim 1, it is characterized in that:
Described chromatographic column filler is repeatedly pushed chromatographic column slowly, chromatographic column is vertically placed, tamp until gel and reach the chromatographic column packing height and do not have bubble.
6. according to the separation method of the carbon nanotube of claim 3, it is characterized in that:
Described chromatographic column is normal pressure or the medium pressure chromatography post of mm of (200-300) mm * (8-20);
Described chromatographic column filler is repeatedly pushed chromatographic column slowly, chromatographic column is vertically placed, tamp until gel and reach the chromatographic column packing height and do not have bubble.
7. according to the separation method of the carbon nanotube of one of claim 1～6, it is characterized in that described separation method comprises the steps:
(1) carbon nanotube mother liquor preparation
With the dispersion Single Walled Carbon Nanotube and the anion surfactant thorough mixing of non-modified to be separated is that Single Walled Carbon Nanotube target volume concentration is the mixture of 0.02-1.0mg/mL, through 400kW ultra-sonic dispersion after 2～6 hours, centrifugation goes out upper strata liquid as the carbon nanotube mother liquor that carries out gel chromatography separation again;
(2) gel chromatography separation
Adopting the anion surfactant of 0.5-3 wt% is moving phase, and flow rate pump 0.1mL/min-0.5mL/min washed populated gel chromatographic columns 1 hour;
In gel chromatographic columns, add the carbon nanotube mother liquor that 0.2mL-5mL step (1) obtains, adopting the anion surfactant of 0.5-3wt% is moving phase, flow rate pump 0.1-0.5mL/min, collect sample at set intervals, collected 0.5-3 hour, and obtained the carbon nanotube of different lengths and semiconductive.
8. according to the separation method of the carbon nanotube of claim 7, it is characterized in that:
In the preparation of described (1) carbon nanotube mother liquor
With the dispersion carbon nanotube of non-modified to be separated and the sodium lauryl sulphate or the Sodium desoxycholate thorough mixing of concentration 1.5% is that Single Walled Carbon Nanotube target volume concentration is the mixture of 0.3 mg/mL, through 400kW ultra-sonic dispersion after 5 hours, centrifugation goes out upper strata liquid as the carbon nanotube mother liquor that carries out gel chromatography separation again.
9. according to the separation method of the carbon nanotube of claim 7, it is characterized in that:
In described (2) gel chromatography separation
At first adopting sodium lauryl sulphate or the Sodium desoxycholate of 0.5-3 wt% is moving phase, and flow rate pump 0.1mL/min washed populated gel chromatographic columns 1 hour;
In gel chromatographic columns, add the carbon nanotube mother liquor that 2mL step (1) obtains, the sodium lauryl sulphate or the Sodium desoxycholate of employing 1.5% are moving phase, and flow rate pump 0.1mL/min collects sample at set intervals, collected 1 hour, and obtained the carbon nanotube of different lengths and semiconductive.
10. the separation method of carbon nanotube according to Claim 8 is characterized in that:
In described (2) gel chromatography separation
At first adopting sodium lauryl sulphate or the Sodium desoxycholate of 0.5-3 wt% is moving phase, and flow rate pump 0.1mL/min washed populated gel chromatographic columns 1 hour;
In gel chromatographic columns, add the carbon nanotube mother liquor that 2mL step (1) obtains, the sodium lauryl sulphate or the Sodium desoxycholate of employing 1.5% are moving phase, and flow rate pump 0.1mL/min collects sample at set intervals, collected 1 hour, and obtained the carbon nanotube of different lengths and semiconductive.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104118857A (en) * | 2013-04-26 | 2014-10-29 | 中国计量科学研究院 | Method used for automatic continuous chromatographic separation of single-walled carbon nanotubes |
| CN104692358B (en) * | 2015-02-16 | 2019-03-15 | 中国科学院物理研究所 | Carbon nanotube separation method |
| CN111615415A (en) * | 2017-10-12 | 2020-09-01 | 弗朗索瓦·帕门蒂尔 | Chromatography method |
-
2011
- 2011-03-18 CN CN 201110066035 patent/CN102219205A/en active Pending
Non-Patent Citations (1)
| Title |
|---|
| 《Applied Physics Express》 20091127 Takeshi Tanaka et al. Continuous Separation of Metallic and Semiconducting Carbon Nanotubes Using Agarose Gel 125002 1-10 第2卷, * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104118857A (en) * | 2013-04-26 | 2014-10-29 | 中国计量科学研究院 | Method used for automatic continuous chromatographic separation of single-walled carbon nanotubes |
| CN104118857B (en) * | 2013-04-26 | 2017-04-26 | 中国计量科学研究院 | Method used for automatic continuous chromatographic separation of single-walled carbon nanotubes |
| CN104692358B (en) * | 2015-02-16 | 2019-03-15 | 中国科学院物理研究所 | Carbon nanotube separation method |
| CN111615415A (en) * | 2017-10-12 | 2020-09-01 | 弗朗索瓦·帕门蒂尔 | Chromatography method |
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Application publication date: 20111019 |